Implementation of the sectional aerosol module SALSA2.0 into the PALM model system 6.0: model development and first evaluation

Urban pedestrian-level air quality is a result of an interplay between turbulent dispersion conditions, background concentrations, and heterogeneous local emissions of air pollutants and their transformation processes. Still, the complexity of these interactions cannot be resolved by the commonly used air quality models. By embedding the sectional aerosol module SALSA2.0 into the large-eddy simulation model PALM, a novel, high-resolution, urban aerosol modelling framework has been developed. The first model evaluation study on the vertical variation of aerosol number concentration and size distribution in a simple street canyon without vegetation in Cambridge, UK, shows good agreement with measurements, with simulated values mainly within a factor of 2 of observations. Dispersion conditions and local emissions govern the pedestrian-level aerosol number concentrations. Out of different aerosol processes, dry deposition is shown to decrease the total number concentration by over 20&thinsp;%, while condensation and dissolutional increase the total mass by over 10&thinsp;%. Following the model development, the application of PALM can be extended to local- and neighbourhood-scale air pollution and aerosol studies that require a detailed solution of the ambient flow field.</p

Multi-year statistical and modeling analysis of submicrometer aerosol number size distributions at a rain forest site in Amazonia

The Amazon Basin is a unique region to study atmospheric aerosols, given their relevance for the regional hydrological cycle and the large uncertainty of their sources. Multi-year datasets are crucial when contrasting periods of natural conditions and periods influenced by anthropogenic emissions. In the wet season, biogenic sources and processes prevail, and the Amazonian atmospheric composition resembles preindustrial conditions. In the dry season, the basin is influenced by widespread biomass burning emissions. This work reports multi-year observations of high time resolution submicrometer (10-600 nm) particle number size distributions at a rain forest site in Amazonia (TT34 tower, 60 km NW from Manaus city), between 2008 and 2010 and 2012 and 2014. The median particle number concentration was 403 cm(-3) in the wet season and 1254 cm(-3) in the dry season. The Aitken mode (similar to 30-100 nm in diameter) was prominent during the wet season, while the accumulation mode (similar to 100-600 nm in diameter) dominated the particle size spectra during the dry season. Cluster analysis identified groups of aerosol number size distributions influenced by convective downdrafts, nucleation events and fresh biomass burning emissions. New particle formation and subsequent growth was rarely observed during the 749 days of observations, similar to previous observations in the Amazon Basin. A stationary 1-D column model (ADCHEM Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer model) was used to assess the importance of the processes behind the observed diurnal particle size distribution trends. Three major particle source types are required in the model to reproduce the observations: (i) a surface source of particles in the evening, possibly related to primary biological emissions; (ii) entrainment of accumulation mode aerosols in the morning; and (iii) convective downdrafts transporting Aitken mode particles into the boundary layer mostly during the afternoon. The latter process has the largest influence on the modeled particle number size distributions. However, convective downdrafts are often associated with rain and, thus, act as both a source of Aitken mode particles and a sink of accumulation mode particles, causing a net reduction in the median total particle number concentrations in the surface layer. Our study shows that the combination of the three mentioned particle sources is essential to sustain particle number concentrations in Amazonia.Peer reviewe

Diesel soot aging in urban plumes within hours under cold dark and humid conditions

Fresh and aged diesel soot particles have different impacts on climate and human health. While fresh diesel soot particles are highly aspherical and non-hygroscopic, aged particles are spherical and hygroscopic. Aging and its effect on water uptake also controls the dispersion of diesel soot in the atmosphere. Understanding the timescales on which diesel soot ages in the atmosphere is thus important, yet knowledge thereof is lacking. We show that under cold, dark and humid conditions the atmospheric transformation from fresh to aged soot occurs on a timescale of less than five hours. Under dry conditions in the laboratory, diesel soot transformation is much less efficient. While photochemistry drives soot aging, our data show it is not always a limiting factor. Field observations together with aerosol process model simulations show that the rapid ambient diesel soot aging in urban plumes is caused by coupled ammonium nitrate formation and water uptake.Peer reviewe

Long term measurements of aerosol optical properties at a primary forest site in Amazonia

A long term experiment was conducted in a primary forest area in Amazonia, with continuous in-situ measurements of aerosol optical properties between February 2008 and April 2011, comprising, to our knowledge, the longest database ever in the Amazon Basin. Two major classes of aerosol particles, with significantly different optical properties were identified: coarse mode predominant biogenic aerosols in the wet season (January–June), naturally released by the forest metabolism, and fine mode dominated biomass burning aerosols in the dry season (July–December), transported from regional fires. Dry particle median scattering coefficients at the wavelength of 550 nm increased from 6.3 Mm−1 to 22 Mm−1, whereas absorption at 637 nm increased from 0.5 Mm−1 to 2.8 Mm−1 from wet to dry season. Most of the scattering in the dry season was attributed to the predominance of fine mode (PM2) particles (40–80% of PM10 mass), while the enhanced absorption coefficients are attributed to the presence of light absorbing aerosols from biomass burning. As both scattering and absorption increased in the dry season, the single scattering albedo (SSA) did not show a significant seasonal variability, in average 0.86 ± 0.08 at 637 nm for dry aerosols. Measured particle optical properties were used to estimate the aerosol forcing efficiency at the top of the atmosphere. Results indicate that in this primary forest site the radiative balance was dominated by the cloud cover, particularly in the wet season. Due to the high cloud fractions, the aerosol forcing efficiency absolute values were below −3.5 W m−2 in 70% of the wet season days and in 46% of the dry season days. Besides the seasonal variation, the influence of out-of-Basin aerosol sources was observed occasionally. Periods of influence of the Manaus urban plume were detected, characterized by a consistent increase on particle scattering (factor 2.5) and absorption coefficients (factor 5). Episodes of biomass burning and mineral dust particles advected from Africa were observed between January and April, characterized by enhanced concentrations of crustal elements (Al, Si, Ti, Fe) and potassium in the fine mode. During these episodes, median particle absorption coefficients increased by a factor of 2, whereas median SSA values decreased by 7%, in comparison to wet season conditions

Modeling the role of highly oxidized multifunctional organic molecules for the growth of new particles over the boreal forest region

In this study, the processes behind observed new particle formation (NPF) events and subsequent organicdominated particle growth at the Pallas AtmosphereEcosystem Supersite in Northern Finland are explored with the one-dimensional column trajectory model ADCHEM. The modeled sub-micron particle mass is up to similar to 75% composed of SOA formed from highly oxidized multifunctional organic molecules (HOMs) with low or extremely low volatility. In the model the newly formed particles with an initial diameter of 1.5 nm reach a diameter of 7 nm about 2 h earlier than what is typically observed at the station. This is an indication that the model tends to overestimate the initial particle growth. In contrast, the modeled particle growth to CCN size ranges (> 50 nm in diameter) seems to be underestimated because the increase in the concentration of particles above 50 nm in diameter typically occurs several hours later compared to the observations. Due to the high fraction of HOMs in the modeled particles, the oxygen-to-carbon (O V C) atomic ratio of the SOA is nearly 1. This unusually high O V C and the discrepancy between the modeled and observed particle growth might be explained by the fact that the model does not consider any particle-phase reactions involving semi-volatile organic compounds with relatively low O V C. In the model simulations where condensation of low-volatility and extremely low-volatility HOMs explain most of the SOA formation, the phase state of the SOA (assumed either liquid or amorphous solid) has an insignificant impact on the evolution of the particle number size distributions. However, the modeled particle growth rates are sensitive to the method used to estimate the vapor pressures of the HOMs. Future studies should evaluate how heterogeneous reactions involving semi-volatility HOMs and other less-oxidized organic compounds can influence the SOA composition-and size-dependent particle growth.Peer reviewe

Evaporation of sulfate aerosols at low relative humidity

Evaporation of sulfuric acid from particles can be important in the atmospheres of Earth and Venus. However, the equilibrium constant for the dissociation of H2SO4 to bisulfate ions, which is the one of the fundamental parameters controlling the evaporation of sulfur particles, is not well constrained. In this study we explore the volatility of sulfate particles at very low relative humidity. We measured the evaporation of sulfur particles versus temperature and relative humidity in the CLOUD chamber at CERN. We modelled the observed sulfur particle shrinkage with the ADCHAM model. Based on our model results, we conclude that the sulfur particle shrinkage is mainly governed by H2SO4 and potentially to some extent by SO3 evaporation. We found that the equilibrium constants for the dissociation of H2SO4 to HSO4-(KH2SO4) and the dehydration of H2SO4 to SO3 ((x) K-SO3) are K H2SO4 = 2-4 x 10(9) mol kg(-1) and (x) K SO3 >= 1.4 x 10(10) at 288.8 +/- 5 K.Peer reviewe

Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of <i>S</i>=0.10–0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. <br><br> The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of &kappa;&asymp;0.1–0.4 (0.16&plusmn;0.06 arithmetic mean and standard deviation). The overall median value of &kappa;&asymp;0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (&kappa;&asymp;0.1 at <i>D</i>&asymp;50 nm; &kappa;&asymp;0.2 at <i>D</i>&asymp;200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. <br><br> The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (<i>f</i>_org) was on average as high as ~90% in the Aitken mode (<i>D</i>&le;100 nm) and decreased with increasing particle diameter in the accumulation mode (~80% at <i>D</i>&asymp;200 nm). The κ values exhibited a negative linear correlation with <i>f</i>_org (<i>R</i>²=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: &kappa;_org&asymp;0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and &kappa;_inorg&asymp;0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (&kappa;_p=&kappa;_org&times;<i>f</i>_org +&kappa;_inorg&times;<i>f</i>_inorg). The CCN number concentrations predicted with &kappa;_p were in fair agreement with the measurement results (~20% average deviation). The median CCN number concentrations at <i>S</i>=0.1–0.82% ranged from <i>N</i>_CCN,0.10&asymp;35 cm^&minus;3 to <i>N</i>_CCN,0.82&asymp;160 cm^&minus;3, the median concentration of aerosol particles larger than 30 nm was <i>N</i>_CN,30&asymp;200 cm^&minus;3, and the corresponding integral CCN efficiencies were in the range of <i>N</i>_CCN,0.10/<i>N</i>_CN,30&asymp;0.1 to <i>N</i>_CCN,0.82/<i>N</i>_CN,30&asymp;0.8. <br><br> Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of <i>N</i>_CCN,<i>S</i> assuming an approximate global average value of &kappa;&asymp;0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded ~50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (&le;100 cm^&minus;3). Model calculations assuming a constant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: ~60% for the campaign average distribution and ~1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. <br><br> Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models

Implementing detailed nucleation predictions in the Earth system model EC-Earth3.3.4: sulfuric acid–ammonia nucleation

Representing detailed atmospheric aerosol processes in global Earth system models (ESMs) has proven to be challenging from both a computational and a parameterization perspective. The representation of secondary organic aerosol (SOA) formation and new particle formation (NPF) in large ESMs is generally constructed with low detail to save computational costs. The simplification could result in losing the representation of some processes. In this study, we test and evaluate a new approach for improving the description of NPF processes in the ESM EC-Earth3 (ECE3) without significant additional computational burden. The current NPF scheme in EC-Earth3.3.4 is derived from the nucleation of low-volatility organic vapors and sulfuric acid (H2SO4) together with a homogeneous water–H2SO4 nucleation scheme. We expand the existing schemes and introduce a new lookup table approach that incorporates detailed formation rate predictions through molecular modeling of sulfuric acid–ammonia nucleation (H2SO2–NH3). We apply tables of particle formation rates for H2SO2–NH3 nucleation, including dependence on temperature, atmospheric ion production rate, and molecular cluster scavenging sink. The resulting differences between using the H2SO4–NH3 nucleation in ECE3 and the original default ECE3 scheme are evaluated and compared with a focus on changes in the aerosol composition, cloud properties, and radiation balance. From this new nucleation scheme, EC-Earth3's global average aerosol concentrations in the sub-100 nm sizes increased by 12 %–28 %. Aerosol concentrations above 100 nm and the direct radiative effect (in W m−2) showed only minor differences upon changing of the nucleation scheme. However, the radiative effect from clouds affected by aerosols from the new nucleation scheme resulted in a global decrease (cooling effect) by 0.28–1 W m−2. The modeled aerosol concentrations were compared to observed measurements at various stations. In most cases, the new NPF predictions (H2SO2–NH3) performed better at stations where previous underestimations for aerosol concentrations occurred.</p

A modelling study of OH, NO3 and H2SO4 in 2007– 2018 at SMEAR II, Finland : analysis of long-term trends

Major atmospheric oxidants (OH, O3 and NO3) dominate the atmospheric oxidation capacity, while H2SO4 is considered as a main driver for new particle formation. Although numerous studies have investigated the long-term trend of ozone in Europe, the trends of OH, NO3 and H2SO4 at specific sites are to a large extent unknown. The one-dimensional model SOSAA has been applied in several studies at the SMEAR II station and has been validated by measurements in several projects. Here, we applied the SOSAA model for the years 2007–2018 to simulate the atmospheric chemical components, especially the atmospheric oxidants OH and NO3, as well as H2SO4 at SMEAR II. The simulations were evaluated with observations from several shorter and longer campaigns at SMEAR II. Our results show that daily OH increased by 2.39% per year and NO3 decreased by 3.41% per year, with different trends of these oxidants during day and night. On the contrary, daytime sulfuric acid concentrations decreased by 2.78% per year, which correlated with the observed decreasing concentration of newly formed particles in the size range of 3– 25 nm with 1.4% per year at SMEAR II during the years 1997–2012. Additionally, we compared our simulated OH, NO3 and H2SO4 concentrations with proxies, which are commonly applied in case a limited number of parameters are measured and no detailed model simulations are available.Peer reviewe